Metalliferous azo-dyestuffs



United States Patent 2,897,190 METALLIFEROUS AZO-DYESTUFFS Alfred Fasciati, Bottmingen, Switzerland, assignor to (Ziba Limited, Basel, Switzerland, a Swiss firm No Drawing. Application October 17, 1955 Serial No. 541,042

Claims priority, application Switzerland December 21, 31951 7 :Claims. '=(Cl. 260-147) in which R represents a benzene radical bound to the azo linkage in *ortho-position to the hydroxyl group, R represents the radical of a coupling component bound to the azo linkage in va position vicinal to a -'hydroxyl group, n represents a whole number not greater than 7, m represents the 'whole number 1 or '2, and X represents a benzene radical containing the aforesaid single carboxylic acid group.

The monoazo-dyestuiis of the above formula serving as starting materials in thepresent process can be made by coupling a coupling-component free from sulfonic acid groups and carboxylic acid'groups and capable of coupling in a'p'osition 'v'icinal -to a hydroxyl group, with a diazotized amine free from sulfonic acid groups and corresponding to the'general 'formula which contains in the radical X a carboxylic acid group which is not present in a position vicinal to a ,hydroxyl or -NH group, the symbols .R n, m and X having the meanings given in connection with Formula 1.

The benzene radical R 'ofth'ese amines, which contains the aminoigroup in .the 2-.position andihehydroxyl ,group in the 1-position may be bound to the-SO group in the 4-, 5- or fi-position. It may contain further substituents incapable of salt formation, for example, an alkyl, alkoxy or acylam'ino group, a halogen atom or a nitro group. The benzene radicaLX :may in addition to the carboxylic acid group contain further substituents incapable of salt formation, such as an alkyl group (for example, methyl), a methoxy group, a chlorine atom or the like, but no salt forming substituents, such as the amino or the hydroxyl group.

As amines of the Formula 2 there may be mentioned:

.2 Z-aniino-l hydroxy-6-chlorobenzene-4-su1fonic acid phenylamide-2-carboxy1ic acid, .2 aminml-hydroxy-6-nit-robenzenel-sulfonic acid phenylamide-Z-carboxylic acid, 2 arnino-l hydroxybenzene-4- or -5-sulfonic acid N-methylphenylamide-Z ,'-carboxy1ic acid,- Z-amino-l-hydroxybenzene 4- or -5- sulfonic acid phenylamide-2-, -3- or -4carboxylic acid, 2-amino-4-chloro-l-hydroxybenzene-S- or -6-sulfonicacid phenylamide-Z-carboxylic acid, 3-amino- 4hydroxydiphenylsulfone-2'-carboxylic acid and 4-ami no-3-hydroxy diphenylsulfone-2-- or -4' -carboxylic acid.

As coupling components for preparing the monoazo- .dyestuifs serving as starting materials in the present process there come into consideration hydroxy-compounds which are capable of coupling in a position vicinal to the hydroxyl group. 'By hydroxy-compounds there are to be understood aromatic hydroxy-compounds as well .as .compounds which owe their capacity for coupling to the :presence -of a keto-methylene group. The latter com- ,pounds may contain the 'keto-methylene group either in an open chain or in a 'heterocyclic :ring.

As hydroxy-compounds of the aforesaid kind there ;-rnay :be mentioned: Para-substituted hydroxybenzenes .-such-:as 4-,methyl-, 3:-4-.dimethyl-, 4-tertiary-amylor 4- acetylamino-lhydroxybenzene and 4-rnethyl-2-acetylamino-l-hydroxybenzene. Di-hydroxybenzenes such as resorcinol, and especially hydroxynaphthalenes and S-pyrazolones such as 2-hydroxynaphthalene, 2:6-dihydroxynaphthalene, 2-hydroxy-6-bromo- -or -6-met-hoxynaph- -thalene, Z-hydroxynaphthalene-6-sulfonic acid anilide, 2-

hydroxynaphthalene-6- or -7-sulfonic acid phenyl ester and l-hydroxy-4-methylnaphthalene, l-hydroxy-S-chloronaphthalene, 1 -7hydroxy 5 :8 dichloronaphthalene, and :also 1-hydroxy-naphthalene-3-, --4- or -5-sulfonic acid isovpropylamide; pyrozolones such .as 3-methylor 3-,phenyl- '5-pyr-azolone, l-n-butyl 'a-methyl-5-pyrazolone, l-phenylyl-) 1phenyl-3-methyl 5epyrazolone, 5 -pyrazolone-3-carboxylic acid amides such as 5-pyrazolone-3-carboxylic acid amide, 5-pyrazolone-3-carboxylic acid -Nmethyl-,

-ethyl-., isopropylor -butylamide, 5-.pyrazolone-3-car'boxylic acid-2 -3- or -4-chlorophenylamide, 5-pyrazolone- ,3-carboxylic acid-phenylor .para-methylphenylamide, 1

--phenyl-'5-pyrazolone-3-carboxylic acid amide, l-phenyl-S- zpyrazolone-3-carboxylic acid methyl-, -isopropyl-, -pheni-yl-or para-'chlorophenylam'ide.

The amines of the Formula 2 may be diazotized in the usual manner, for example, with-the use of sodium nitrite and hydrochloric acid. Coupling of the resulting diazo compounds with the aforesaid coupling components can alsoibe carried out in the usual manner.

When the coupling reaction is finished the dyestuffs can be separated from the coupling mixture easily by :gram-atom of metal for every two molecular proportions of a dyestuif of the general Formula 1 or for about one molecular proportion of each two ditferent monoazodyestuffs free from sulfonic acid groups in a mixture of such dyestufis of which at least one corresponds to the general Formula 1, and/or to carry out the metalli'zation in a weakly acid to alkaline medium. Accordingly, there are especially suitable, for example, those metal com pounds which are stable to alkaline media, for example, chromium compounds of aliphatic ortho-hydroxy-carboxylic acids, or chromium compounds of aromatic orthohydroxycarboxylic acids, which compounds contain the metal in complex union. As examples of aliphatic hydroxycarboxylic acids there may be mentioned inter alia lactic acid, glycollic acid, citric acid and especially tartaric acid, and among the aromatic hydroxycarboxylic acids there may be mentioned those of the benzene series such as 4-, 5- or 6-methyl-l-hydroxybenzene-2-carboxylic acid and above all l-hydroxybenzene-Z-carboxylic acid itself. Conversion of the dyestuffs into their complex metal compounds is advantageously carried out at a raised temperature, under atmospheric or superatmos pheric pressure, for example, at the boiling temperature of the reaction mixture, if desired in the presence of suitable additions, for example, in the presence of salts of organic acids, bases, organic solvents or other agents assisting the formation of complexes.

The metalization treatment described above may be applied, for example, to a single dyestutf of the Formula 1. However, it is also possible and is in many cases of advantage (for example, in order to produce different tints) to metallize a mixture of two different dyestuffs of that formula or a mixture consisting of a dyestufi of the said formula and another metallizable monoazo-dyestufi free from sulfonic acid and advantageously also free from carboxylic acid groups, for example, an ortho:ortho-dihydroxy-monoazo-dyestuff.

The monoazo-dyestuifs to be used as starting materials in the last mentioned form of the process together with dyestuffs of the Formula 1, may be of any desired constitution provided that they are free from sulfonic acid 'methyl-Z-amine-l-hydroxybenzene, 2 amino-l-hydroxybenZene-4- or -5-sulfonic acid amide, and the corresponding N-methyl-, -ethyl-, -isopropyl-, -octyl-, -cyclohexyl-, phenyl-, para-chlorophenyl-amides, and also 2-amino-1- hydroxybenzene-4- or -5-sulfonic acid dimethylamide or N-methylphenylamide, Z-amino-1-hydroxy-benzene-4- or -5-methylsulfone, 3amino-4-hydroxy-diphenylsulfone, 4 amino3 -hydroxydiphenylsulfone, and also 5-nitro-2-amino-l -hydroxybenzene, 2-aminobenzene-1-carboxylic acid, 2-aminobenzene-l-carboxylic acid-S-sulfonic acid methylor -phenyl-amide, 2-aminobenzene-l-carboxylic acid-5- 4 methyl-sulfone and Z-aminobenzene-l-carboxylic acid-5- sulfonic acid phenyl ester.

The chromium compounds so obtained contain two monoabo-dyestuff molecules bound to one atom of chromium in complex union, and at least one of the monoazodyestufi molecules must correspond to the general Formu- 1a 1. The new chromium compounds are soluble in water, and are indeed more soluble than the starting materials used for making them. They are suitable or dyeing various substances such as plastic masses, waxes, resins, lacquers and the like and especially for dyeing or printing synthetic substances composed of superpolyamides or superpolyurethanes, and above all for dyeing or printing animal materials such as silk, leather and especially wool. They are suitable for dyeing from a weakly alkaline or neutral bath, and above all from a weakly acid, for example, acetic acid bath.

The dyeings so produced are distinguished by their good level character, good properties of wet fastness and very good fastness to light.

The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter:

Example I 30.8 parts of 1-hydroxy-2-aminobenzene-4-sulfonic acid-phenylarnide-2'-carboxylic acid are dissolved in 150 parts of water and 22 parts of a 10 N-solution of caustic soda. The resulting clear solution is mixed with 25 parts of a 4 N-solution of sodium nitrite, and introduced dropwise at 0-2 C. into a mixture of parts of water and 40 parts of 10 N-hydrochloric acid. The resulting pale yellow diazo suspension is neutralized with sodium carbonate, and added to an ice cooled solution of 22.9 parts of 1-(4'-chlorophenyl)-3-methyl-5pyrazolone in parts of water, 10 parts of a 10 N-solution of caustic soda and 15 parts of sodium carbonate. When the coupling is finished the dyestuff is completely precipitated by the addition of sodium chloride and filtered off.

One half of the dyestufi so obtained is suspended in 750 parts of Water, and boiled under reflux with 75 parts of a chromium-sodium salicylate solution containing 2.67 percent of chromium for several hours. The resulting solution is neutralized by the addition of acetic acid, and the chromium complex formed is'precipitated by the addition of sodium chloride, filtered off and dried.

When dry it is a red-brown substance which dissolves in dilute sodium carbonate solution with a yellow-brown coloration and in pure concentrated sulfuric acid with a yellow coloration, and dyes Wool from a neutral or acetic acid bath very fast orange tints.

In the following table are given the properties of further complex chromium compounds obtainable in an analogous manner. In column (a) is given the tint of the dyeings produced on wool or fibers of a superpolyamide with the chromium complex of the dyestuff obtained from the components given in columns I and II.

Diazo component Coupling component Chromium complex 9 NH, @011 Violet grey.

smNHOo on OH EC) 01 10..-. NH; Blue grey.

C O 0H OH I 11...-- N H: I OH Violet grey.

12"--. NH} H2O Scarlet.

o N o=h G O OH 13.. NH: H1O l Orange.

3: o 0 OH Example 2 acid group, which monoazo dyestufi corresponds to the 2 parts of the chromiferous dyestutf obtained as described in Example 1 are dissolved in 4000 parts of water, parts of crystalline sodium sulfate are added and 100 parts of well wetted wool are entered into the resulting dyebath at -50 C. 2 parts of acetic acid of 40 percent strength are then added, the temperature is raised to the boil in the course of /2 hour, and dyeing is carried on at the boil for hour. Finally the wool is first rinsed with cold water and dried. The wool is dyed a orange tint of good fastness especially to light.

The same dyeing is obtained by dyeing from a neutral bath, that is to say without the addition of acetic acid to the bath.

What is claimed is:

1. A complex chromium compound containing one atom of chromium bound in complex union with substantially two molecules of a monoazo dyestufi free from sulfonic acid groups and containing a single carboxylic formula wherein R represents a benzene radical bound to the azo linkage in ortho-position relatively to the hydroxyl group, R represents the radical of a coupling component selected from the group consisting of a S-pyrazolone bound to the azo linkage in 4-position, a chlorinated l-hydroxynaphthalene bound to the azo linkage in 2-position, and a Z-hydroxynaphthalene bound to the azo linkage in l-posi- 'tion and containing at most as single substituent a bromine atom, 12 represents a whole number up to 7, m a whole number up to 2 and X a benzene radical which contains as single salt forming group the said carboxylic acid group.

2. A complex chromium compound containing one atom of chromium bound in complex union to substantially two molecules of a monoazo dyestufi of the formula wherein Pz represents a S-pyrazolone radical free from sulfonic and carboxylic acid groups and bound to the azo linkage in 4-position, which radical contains a chlorophenyl radical.

3. A complex chromium compound containing one atom of chromium bound in complex union to substantially two molecules of a monoazo dyestuff of the formula a e-NE OOOH wherein R represents a chlorinated l-hydroxynaphthalene radical bound to the azo linkage in 2-posit-ion and free from sulfonic and carboxylic acid groups.

4. The complex chromium compound containing one atom of chromium bound in complex union with substantially two molecules of the monoazo dyestuft' of the formula 5. The complex chromium compound containing one atom of chromium bound in complex union with substantially two molecules of the monoazo dyestufi' of the formula Or-NILQ 6. The complex chromium compound containing one atom of chromium bound in complex union with substantially two molecules of the monoazo dyestuff of the formula OH HO C1 SOs-NH 1 OOOH 7. The complex chromium compound containing one atom of chromium bound in complex union with substantially two molecules of the monoazo dyestuif of the References Cited in the file of this patent UNITED STATES PATENTS 1,814,218 Holzach et a1. July 14, 1931 2,597,676 Schetty May 20, 1952 2,634,263 Steinemann Apr. 7, 1953 OTHER REFERENCES Row et a1.: J. Soc. Dyers Colourists, vol. 62, 1946, pp. 372-373.

Weidmann: American Dyestufi Reporter, March 15, 1954, p. 167. 

1. A COMPLEX CHROMIUM COMPOUND CONTAINING ONE ATOM OF CHROMIUM BOUND IN COMPLEX UNION WITH SUBSTANTIALLY TWO MOLECULES OF A MONOAZO DYESTUFF FREE FROM SULFONIC ACID GROUPS AND CONTAINING A SINGLE CARBOXYLIC ACID GROUP, WHICH MONOAZO DYESTUFF CORRESPONDS TO THE FORMULA 